Production of zirconium



F. H. SPEDDING EIAL PRODUCTION OF ZIRCONIUM Filed Sept. 7, 1951 I June z5, 1957 2,797,160

IN V EN TORS United States of Americans represented by the United States Atomic Energy Commission Application september 7, 1,'95'1, serial No.' 245,4@

s claims. (ci. 7s s4.4)

This invention deals with a process for the production of zirconium and zirconium-base alloys from zirconium halides, in parti-cular from zirconium tetrauoride; Zirconium and zirconium-base metals have Widespread use asconstruction'materials on account of their hardness and corrosion-resistance.

It is an object of this invention to provide a process for producing zirconium metal in pure and massive form.

It is another object of this invention to provide a process for producing zirconium which is -free of oxygen and consequentlyl nonbrittle.

It is another lobject ofl this invention to provide a process for producing'zi-r'c'onium metal ofr great ductility.'

It is another object of this invention to provide a process for producing zirconium metal wherein zirconium is formed in molten form by an instantaneous reaction so thatV the time of extreme heat and thus for possible reaction of the molten zirconium with the Crucible material is reduced. Y

It is also an object of this invention to provide a process for producing zirconium metal in which a low-melting, nonreacting slag is obtained.

These and other objects are accomplished'by preparing a mixture of zirconium tetrafluonde and a reducing metal and heating this mixture in' a closed reactor whereby a regulus of metallic zirconium and .a layer of slag are formed, cooling the reaction products to about roomtemperature, and separating the zirconium from the slag. In carrying out the invention, a so-ca'lled booster material, in particular iodine or sulfur, is added to the reaction mixture; the booster is a ksubstance which reacts with the reducing metal in a reaction more exothermic than that of the reduction' ofthe zirconium tetrauoride. It is very advantageous to add also an alloying metal in the form of a `compound which as such functions as a booster so that with this one compound the dual purpose of furnishing heat and the alloying metal is attained.

Alkali metals and alkalineearth metals are suitable as reducing agents, and in particular magnesium vand calcium have been found to yield satisfactory results.I

Calcium is the preferred reducing metal; it hasjbeen found advisable to use an excess over the stoichiometric quantity necessaryI for the reduction of the zirconium tetrafluoride and also of the booster material. Anexcesls of at least over the stoichiometric quantity is preferredgand about r25% excess is best. yThe calcium or other reducing metal, as wellas all reactants, are advantageously usedV in pure -form in order to obtain a pure zirconium metal or alloy. For this reason calcium metal,y

foninstance,-l is redistilfled .prior to its use. y

- `The Acompound formed from therreducing .metal and the lbooster isadiux by whichv alow-melting slag is se-` is reducedto-a Y g In additonfto loweringl the Vmelting point' of the slag bythe compound formed fromthe booster, it is also adcured so that reaction between'the As/lagand the `crucible vantageous to add an alloying metal to the charge ini order,v

A. Wilhelm, Ames, Iowa,` and Wayne H. Keller,'St.'Louis, Mo., assignors to the nited States Pai-em o 2,797,160 Patented June 25, 1957 to obtain a zirconium alloy of a melting point lower than or jolting. The cap 6 rwith satisfaction for the that ofy zirconium. If zirconium is to Abe iinally obtained in pure metallic form, 'it is wise to choose the al'loying metal so that its removal from the alloy does not cause any diiliculty. Zinc or cadmium metal have been found suitable, zinc being the preferred alloying agent. The addition of an alloying metal has the further advantage that it alloys with the metallic zirconium as it is formed; by this the zirconium yield is increased.

While zinc, for instance, may be added in metallic form, it may also be formed 'during the reaction; for instance, in some cases zinc fluoride or zinc chloride was added to the charge and the quantity of reducing metal accordingly increased so that'the reduction of the zinc liuoride or zinc chloride was secured and a zirconiumzinc alloy was'obta'ined. If, of course, the ai-m of the process is the production of an alloy of speciiic properties, the'alloying metal is preferably chosen correspondingly. Zirconium alloys whichhavetbeen prepared by the process of this invention are those containing any of the following ingredients: Bi, Pb, Pt, V, Cb, Mo, Cr, Pd, Ta," Sn'and V; with the exception of vanadium, which was obtained by coreducing vanadium tuoride, the components were added as the metals.

Zinc chloride and/or zinc iluoride, when used as just described,l also act as an additional booster material; their use is therefore advantageous for the process of this invention. Zinc chloride, which is hygroscopic, is preferably added after being vacuum dried.`

The optimal molal ratio, in the case of iodine as the booster material, for iodine to zirconium tetratiuori'de wasl found to be 0.35 if zinc was present, but 0.75 without the addition of zinc. With these quantities about 98% of the zirconium present were'recovered in metallic form. In the case of sulfur, a molal ratio of from 0.208 to 0.425 yielded an output between -95% with zinc, While without zinc and a molal ratio of 1 (l gram atom of sulfur to l gram mole of ZrF4) a yield of 95-98% was obtained. The excess of calcium was 10% in all these instances. l

The materials are preferably used in disintegrated formA and mixed thoroughly. Particle sizes foundl advantageous, however' not critical, are -100 mesh for zirconium tetrafluoride, l0 mesh for calcium, -20 mesh for iodine, about v100 mesh for sulfur and about 20 mesh for zinc chloride; yzinc has been used with satisfaction in the form of turnings of approximately one-half grain each and a thickness of 0.005 in.

In the attached drawing, an apparatus is illustrated, in a longitudinal sectional view, that has been used process of this invention. In this drawing, the reference numeral 1 indicates a reduction bomb made of a steel pipe of. an inner diameter of 2:5 in, and alength of 13 in. and a welded bottom; The top of the bomb is threaded as indicated at 2. A presintered liner 3 is inserted into this bomb which is formed of electrically fused dolomitic oxide. Calcium oxide and, in some cases, graphite have also been -found suitable as lliner materials. vThe liner has side walls l/s' in. thick and an inner diameter of 2 in. which leaves an inter- This interspace is filled with magnorite 4 whereby the liner is supported sufficiently to avoid Yany mechanical damage during operation. The disintegrated and thoroughly mixed charge`5 Afills the 'liner :almost toits'top; it has: been compacted by .stamping mitic -oxide 7 is screwed to the top by means of threads corresponding to those of the bomb indicated by'ref-A erenceV numeralV 2.

which has been prepacked with dolo-l `'I'he threads of the capv and/or the4 bombrarecoveredwith a ppejoint cement in order'to' warranta-'pressure-tightfseal. Atfthc outside sidewall there is arranged a Well 8 adapted to receive a thermocouple.

Before and/or after the lbomb was packed lwith the charge and prior to sealing, 4the oxygen was removed, for instance, 'by flushing with argon with -or without intermittent evacuation. The sealed bomb was then inserted in the cold state into the pit of a gas-fired furnace which had la temperature of about 700 C. When sulfur was used as the booster, the reaction started after tive minutes which was indicated by a sudden a-cceleration of temperature increase. The temperature `of the reaction mass at that time was approximately 450 C. In the case of an iodineboosterthe reaction started at approximately 550 C. after fourteen minutes of preheating. .It was observed that during the reaction proper a temperature increase of -about 300 per minute took place while a normal heating rate would have `brought about -an increase of 25-50" per minute. After three minutes the entire process was completed. This instantaneous course of the reaction is responsible for a minimum of heat loss.

After the reaction had terminated, the bomb was :allowed to cool to room temperature by taking it out of the furnace; this took approximately one and one-half hours. Thereafter, the material was hammered -out `of the liner or `crucible. At the bottom of the'reaction mass, a regulus of zirconium metal -was usually found of a thickness of about .l in. and there-over a slag layer of about 4 in. thickness. The output in a bomb of the dimensions -described usually ranged from 200-220 g. of zirconium.

A relatively large scale operation was carried out successfully with a bomb constructed similarly to the one described but having an inside diameter of `4 in. and a length of l5 in. 'In this case, the liner was not preformed by sintering but by jolt-packing the electrically fused dolomitic oxide around a mandrel in the bomb; the intermediate layer of magnorite was omitted in this instance. An output of from 700-750 g. of zirconium was accomplished in this larger bomb. The rel-ative yield in this instance was slightly lower, though, because the joltpacked liner had a higher porosity than the presintered oneY and absorbed some of the zirconium formed.

Whether zirconium was obtained in metallic form `or in the form of an alloy, lpurification or separation was necessary in order to remove lforeign yundesirable ingredients. For this purpose, the crude metal was placed into a tantalum cup and the cup into a graphite Crucible; the crucible with the cup `Was then inserted into a quartz envelope, and the entire assembly was heated by induction while applying `a high vacuum. l1`he temperature used was as low as 900 C.; with M00 C. 90% of the zinc was removed. Higher temperatures, such as up to 1700 C. increased the rate of volatilization. Heating to that temperature was carried out relatively `slowly within about one and one-half hours, and the maximum temperature was then maintained for about two and onehalf hours. Under these conditions all volatile ingredients such as zinc, calcium, magnesium, iodine and sulfur were removed. A highly pure metal `was obtained by the distillation process which was immediately usable for casting into the desired sha-pe.

'In the following, a number of preferred embodiments of the process of this invention are described.

Example I `Four hundred grams of `zirconium tetrafluoride, 40 g. of zinc, 64 g. of iodine and 223 g. of calcium metal were thoroughly mixed and filled into the smaller of `the ftwo -bombs described after it had been alternately evacuated and lled with argon gas three times. The bomb was capped and inserted into the gas-heated furnace and' heated for reaction followed by cooling as described Iabove. T he regulus obtained consisted of a zirconiumzinc alloy of a zirconium'content 05.85% by Weight. The

4 total zirconium output amounted to about 97%. Zinc, calcium, etc. werethen removed-by-induction heating in a vacuum. The zirconium metal obtained after vacuum distillation was analyzed land found to contain:

fP. p. m. Al 20-30 B 1.2-3.3 Ca 10-60 Co 10 Cr 10 Cu `10--50 Fe 150-300 C 300-500 Mg 5-15 Ni 10 Si 30l00 Ti 10-'20 Mn 15-25 N 60-175 Zn v5-40 yIt had ahardness of 47 Rockwellyscale A. The identical experiment except that lg. of.zinc were used with otherwise the same amounts of the same ingredients -given above yieldeda moreductile .zirconium metal of a hardness of `4'1 Rockwell, scale A.

Another analogous experiment w-as carried out in the larger ,of the two 'bombs described using a charge of 1400 g. `of zirconium tetrauoride, 140 g. of zinc, 225 g. of iodine and 780 g. of calcium. The operating steps and conditions were identical withthose of the small scale operation. The yield in this instance was.92% of zirconi-um.

Example II Another experiment was carried out in the small laboratory 'bomb Awhich -was analogous to that of Example I but in which sulfur was used as the booster material. The chargeconsisted'of 400 g. of zirconium tetrauoride, 30.9 g. of Azinc, '16 g. of sulfur, and 233 g. of calcium. The yield ranged from 93-917% in various runs, the zirconium again `being obtained as a zirconium-zinc alloy.

`Example Ill Three hundred thirty-one grams of zirconium tetrafluoride, 66 g. of sulfur and 263 g. of calcium were heated as described in theprevious examples. A yield of from 95-98% of zirconium in metallic form was obtained.

Example IV Four hundred grams of zirconiumtetrauoride, 26.9 g. of zinc chloride, 202g. of iodine and 255 g. of calcium were .reacted as described Tabove; they yielded 97% of zirconium in the form `ofa zirconium-zinc alloy.

Three hundred grams of zirconium tetrauoride having a particle-size of mesh were mixed with 338 g. of iodine and 225 g. of calcium. A yield of 99% of zirconium in metallic form was obtained.

While in all the instancesfillustrated above, a yield of above 90% was obtained, experiments'carried out with sulfates, chlorates, and other oxygen-containing salts as the booster developed too high a reaction heat which entailed a number of difficulties including reaction with the liner-and thus made'the operationof the process unsatisfactory.

Substitution of other zirconium halides for the zirconium vtetraiiuoride inthe reduction 'with calcium using iodine or sulfur as the booster was not investigated, because comparative Aexperiments with zinc chloride as booster indicated the inferiority of other halides as compared with zirconium tetrauoride. For instance, reduction of Apotassium'tluorozirconate under-these conditions yielded :an 'outputfof 60% zirconium, and .that of zironium tetrachloride an output of 71%, while the yields of reduction of zirconium tetrauoride with calcium and zinc chloride as booster varied between 90 and 95%.

It will be understood that this invention is not to be limited to the details given herein but that it may be modified within the scope of the appended claims.

This application is a continuation-impart of our copending applications Serial No. 628,652, led November 14, 1945, and Serial No. 695,299, led September 6, 1946, now Patent No. 2,782,116 dated February 19, 1957.

What is claimed is:

1. A process for producing massive zirconium metal, comprising mixing zirconium tetrailuoride, zinc, a reducing metal selected from the group consisting of alkali metals and alkaline earth metals, and a booster substance selected from the group consisting of iodine and sulfur, said reducing metal being used in a quantity excessive of that stoichiometrically required and the molal ratio of booster to zirconium tetrauoride being 0.105 in the case of iodine and from 0.208 to 0.425 in the case of sulfur; heating the mixture thus obtained in a closed system to at least 450 C. whereby a regulus of metallic zirconium and a slag layer form; cooling the reaction products to about room temperature; and separating the zirconium from the slag.

CTI

2. The process of claim l wherein the reducing metal is calcium.

3. The process of claim 2 wherein the calcium is used in an excess of at least 10% of that theoretically required.

4. The process of claim 3 wherein 25% by weight of calcium is used in excess over that stoichiometrically required.

5. The process of claim 2 wherein the booster is iodine.

6. The process of claim 2 wherein the booster is sulfur.

7. The process of claim l wherein the zirconium separated from the slag is subjected to a high vacuum distillation at a temperature up to l700 C. whereby zinc and Volatile impurities are removed.

8. A process for producing zirconium, comprising the steps of mixing 400 parts by weight of zirconium tetratluoride, 40 parts by weight of zinc, 64 parts by weight of iodine and 223 parts by weight of calcium, heating the mixture while excluding oxygen and oxygen-containing materials to at least 450 C., cooling the reaction mixture after completed reaction, mechanically separating a zirconium-zinc alloy formed from a slag formed, and subjecting said alloy to a high-vacuum distillation at about 1700 C.

N o references cited. 

1. A PROCESS FOR PRODUCING MASSIVE ZIRCONIUM METAL, COMPRISING MIXING ZIRCONIUM TETRAFLUORIDE, ZINC, A REDUCING METAL SELECTED FROM THE GROUP CONSISTING OF ALKALI METALS AND ALKALINE EARTH METALS, AND A BOOSTER SUBSTANCE SELECTED FROM THE GROUP CONSISTING OF IODINE AND SULFUR, SAID REDUCING METAL BEING USED IN A QUANTITY EXCESSIVE OF THAT STOICHIOMETRICALLY REQUIRED AND THE MOLAL RATIO OF BOOSTER TO ZIRCONIUM TETRAFLUORIDE BEING 0.105 IN THE CASE OF IODINE AND FROM 0.208 TO 0.425 IN THE CASE OF SULFUR; HEATING THE MIXTURE THUS OBTAINED IN A CLOSED SYSTEM TO AT LEAST 450*C. WHEREBY A REGULUS OF METALLIC ZIRCONIUM AND A LAYER FORM; COOLING THE REACTION PRODUCTS TO ABOUT ROOM TEMPERATURE; AND SEPARATING THE ZIRCONIUM FROM THE SLAG. 